This invention relates to dispersant-viscosity improvers for lubricating oils and fuels, processes for preparing them, additive concentrates, and lubricating oil and fuel compositions.
The viscosity of hydrocarbonaceous liquids, for example fuels and lubricating oils, particularly the viscosity of mineral oil based lubricating oils, is generally dependent upon temperature. As the temperature of the oil is increased, the viscosity usually decreases.
The function of a viscosity improver is to reduce the extent of the decrease in viscosity as the temperature is raised or to reduce the extent of the increase in viscosity as the temperature is lowered, or both. Thus, a viscosity improver ameliorates the change of viscosity of an oil containing it with changes in temperature. The fluidity characteristics of the oil are improved.
Viscosity improvers are usually polymeric materials and are often referred to as viscosity index improvers.
Dispersants are also well-known in the art. Dispersants are employed in lubricants to keep impurities, particularly those formed during operation of mechanical devices such as internal combustion engines, automatic transmissions, etc. in suspension rather than allowing them to deposit as sludge or other deposits on the surfaces of lubricated parts.
Multifunctional additives that provide both viscosity improving properties and dispersant properties are likewise known in the art. Such products are described in numerous publications including Dieter Klamann, xe2x80x9cLubricants and Related Productsxe2x80x9d, Verlag Chemie Gmbh (1984), pp 185-193; C. V. Smalheer and R. K.
Smith, xe2x80x9cLubricant Additivesxe2x80x9d, Lezius-Hiles Co. (1967); M. W. Ranney, xe2x80x9cLubricant Additivesxe2x80x9d, Noyes Data Corp. (1973), pp 92-145, M. W. Ranney, xe2x80x9cLubricant Additives, Recent Developmentsxe2x80x9d, Noyes Data Corp. (1978), pp 139-164; and M. W. Ranney, xe2x80x9cSynthetic Oils and Additives for Lubricantsxe2x80x9d, Noyes Data Corp. 1980), pp 96-166. Each of these publications is hereby expressly incorporated herein by reference.
Dispersant-viscosity improvers are generally prepared by functionalizing, i.e., adding polar groups, to a hydrocarbon polymer.
Hayashi et al, U.S. Pat. No. 4,670,173 relates to compositions suitable for use as dispersant-viscosity improvers made by reacting an acylating reaction product which is formed by reacting a hydrogenated block copolymer and an alpha,beta olefinically unsaturated reagent in the presence of free-radical initiators, then reacting the acylating product with a primary amine and optionally with a polyamine and a mono-functional acid.
Lange, et al, U.S. Pat. No. 4,491,527 relates to ester-heterocycle compositions useful as xe2x80x9clead paintxe2x80x9d inhibitors in lubricants. The compositions comprise derivatives of substituted carboxylic acids in which the substituent is a substantially aliphatic, substantially saturated hydrocarbon based radical containing at least about 30 aliphatic carbon atoms; said derivatives being the combination of: (A) at least one ester of said carboxylic acids in which all the alcohol moieties are derived from at least on mono- or polyhydroxyalkane; and (B) at least one heterocyclic condensation product of said substituted carboxylic acids containing at least one heterocyclic moiety which includes a 5- or 6-membered ring which contains at least two ring hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen separated by a single carbon atom, at least one of said hetero atoms being nitrogen, and at least one carboxylic moiety; the carboxylic and heterocyclic moieties either being linked through an ester or amide linkage or being the same moiety in which said single carbon atom separating two ring hetero atoms corresponds to a carbonyl carbon atom of the substituted carboxylic acid.
Lange, et al, U.S. Pat. No. 5,512,192 teach dispersant viscosity improvers for lubricating oil compositions comprising a vinyl substituted aromatic-aliphatic conjugated diene block copolymer grafted with an ethylenically unsaturated carboxylic acid reacted with at least one polyester containing at least one condensable hydroxy group and at least one polyamine having at least one condensable primary or secondary amino group, and optionally, at least one hydrocarbyl substituted carboxylic acid or anhydride.
Chung et al, U.S. Pat. No. 5,035,821 relates to viscosity index improver-dispersants comprised of the reaction products of an ethylene copolymer grafted with ethylenically unsaturated carboxylic acid moieties, a polyamine having two or more primary amino groups or polyol and a high functionality long chain hydrocarbyl substituted dicarboxylic acid or anhydride.
Van Zon et al, U.S. Pat. No. 5,049,294, relates to dispersant/VI improvers produced by reacting an alpha,beta-unsaturated carboxylic acid with a selectively hydrogenated star-shaped polymer then reacting the product so formed with a long chain alkane-substituted carboxylic acid and with a C1 to C18 amine containing 1 to 8 nitrogen atoms and/or with an alkane polyol having at least two hydroxy groups or with the preformed product thereof.
Bloch et al, U.S. Pat. No. 4,517,104, relates to oil soluble viscosity improving ethylene copolymers reacted or grafted with ethylenically unsaturated carboxylic acid moieties then with polyamines having two or more primary amine groups and a carboxylic acid component or the preformed reaction product thereof.
Gutierrez et al, U.S. Pat. No. 4,632,769, describes oil-soluble viscosity improving ethylene copolymers reacted or grafted with ethylenically unsaturated carboxylic acid moieties and reacted with polyamines having two or more primary amine groups and a C22 to C28 olefin carboxylic acid component.
Lange, U.S. Pat. No. 5,540,851 describes dispersant viscosity improvers for lubricating oil compositions which are the reaction product of (a) an oil soluble ethylene-alpha olefin copolymer wherein the alpha olefin is selected from the group consisting of C3-28 alpha olefins, said polymer having a number average molecular weight ranging from about 30,000 to about 300,000 grafted with an ethylenically unsaturated carboxylic acid or functional derivative thereof; with at least one polyester containing at least one condensable hydroxyl group, and at least one polyamine having at least one condensable primary or secondary amino group, and optionally at least one hydrocarbyl substituted carboxylic acid or anhydride.
Each of these patents is hereby expressly incorporated herein by reference.
For additional disclosures concerning multi-purpose additives and particularly viscosity improvers and dispersants, the disclosures of the following United States patents are incorporated herein by reference:
Many such additives are frequently derived from carboxylic reactants, for example, acids, esters, anhydrides, lactones, and others. Specific examples of commonly used carboxylic compounds used as intermediates for preparing lubricating oil additives include alkyl-and alkenyl substituted succinic acids and anhydrides, polyolefin substituted carboxylic acids, aromatic acids, such as salicylic acids, and others. Illustrative carboxylic compounds are described in Meinhardt, et al, U.S. Pat. No. 4,234,435; Norman et al, U.S. Pat. No. 3,172,892; LeSuer et al, U.S. Pat. No. 3,454,607, and Rense, U.S. Pat. No. 3,215,707.
All of the foregoing patents and publications and all of those mentioned hereinafter are hereby incorporated herein by reference.
Many carboxylic intermediates used in the preparation of lubricating oil additives contain chlorine. While the amount of chlorine present is often only a very small amount of the total weight of the intermediate, the chlorine frequently is carried over into the carboxylic derivative which is desired as an additive. For a variety of reasons, including environmental reasons, the industry has been making efforts to reduce or to eliminate chlorine from compositions designed for use as lubricant or fuel additives.
Accordingly, it is desirable to provide low chlorine or chlorine free derivatives for use as additives in lubricants.
A further object is to provide processes for preparing such additives.
Other objects will in part be obvious in view of this disclosure and will in part appear hereinafter.
This invention relates to a composition comprising a hydrocarbon polymer having {overscore (M)}n ranging from 20,000 to about 500,000, when the polymer is not a star polymer, and up to about GPC peak molecular weight of 4,000,000 when the polymer is a star polymer having attached thereto pendant groups Aa and Bb wherein each A is independently selected from members of the group consisting of: groups of the formula 
wherein R3 is H or hydrocarbyl, R4 is a divalent hydrocarbylene group, n=0 or 1, and each of R9 and R10 is independently H, alkoxyhydrocarbyl, hydroxyhydrocarbyl, hydrocarbyl, aminohydrocarbyl, N-alkoxyalkyl- or hydroxyalkyl-substituted aminohydrocarbyl, or a group of the formula "Parenopenst"Y"Parenclosest"cR11xe2x80x94M, wherein each Y is independently a group of the formula 
each R11 is a divalent hydrocarbyl group, R12 is as defined above for R9 and R10, and M is H, hydrocarbyl, amino, xe2x80x94OH, an amide group, an amide-containing group, an acylamino group, an imide group, a heterocyclic group, an imide-containing group, or, xe2x80x94SRxe2x80x2, wherein Rxe2x80x2 is H or hydrocarbyl, and c is 0 or a number ranging from 1 to about 100, or one of R9 and R10 taken together with the adjacent N constitute a Nxe2x80x94N group; and each B is independently selected from members of the group of formula:
wherein each X is independently O, S, or NRb, each Rb is independently H, NH2, hydrocarbyl, hydroxy-hydrocarbyl or aminohydrocarbyl, and each Z is independently a group of the formula 
wherein
each of R3, R4, and n is as defined hereinabove;
each Ra is independently an ethylene group, a propylene group, which groups optionally have hydrocarbyl or hydroxyhydrocarbyl substituents, or 
wherein J is H, SH, NH2, or OH, and tautomers thereof; the subscript a is 0 or a number ranging from 1 to about 50, and the subscript b is a number ranging from 1 to about 30. Preferably, no more than three of R9, R10 and R12 contain amide groups, imide-containing groups, acylamino groups or amide-containing groups.
As used herein, the terms xe2x80x9chydrocarbonxe2x80x9d, xe2x80x9chydrocarbylxe2x80x9d or xe2x80x9chydrocarbon basedxe2x80x9d mean that the group being described has predominantly hydrocarbon character within the context of this invention. These include groups that are purely hydrocarbon in nature, that is, they contain only carbon and hydrogen. They may also include groups containing substituents or atoms which do not alter the predominantly hydrocarbon character of the group. Such substituents may include halo-, alkoxy-, nitro-, etc. These groups also may contain hetero atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen and oxygen. Therefore, while remaining predominantly hydrocarbon in character within the context of this invention, these groups may contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms provided that they do not adversely affect reactivity or utility of the process or products of this invention.
In general, no more than about three non-hydrocarbon substituents or hetero atoms, and preferably no more than one, will be present for every 10 carbon atoms in the hydrocarbon or hydrocarbon based groups. Most preferably, the groups are purely present in a chain or ring otherwise composed of carbon atoms provided that they do not adversely affect reactivity or utility of the process or products of this invention.
In general, no more than about three non-hydrocarbon substituents or hetero atoms, and preferably no more than one, will be present for every 10 carbon atoms in the hydrocarbon or hydrocarbon based groups. Most preferably, the groups are purely hydrocarbon in nature, that is, they are essentially free of atoms other than carbon and hydrogen.
Throughout the specification and claims the expression oil soluble or dispersible is used. By oil soluble or dispersible is meant that an amount needed to provide the desired level of activity or performance can be incorporated by being dissolved, dispersed or suspended in an oil of lubricating viscosity. Usually, this means that at least about 0.001% by weight of the material can be incorporated into a lubricating oil. For a further discussion of the terms oil soluble and dispersible, particularly xe2x80x9cstably dispersiblexe2x80x9d, see U.S. Pat. No. 4,320,019 which is expressly incorporated herein by reference for relevant teachings in this regard.
The expression xe2x80x9clowerxe2x80x9d is used throughout the specification and claims. As used herein to describe various groups, the expression xe2x80x9clowerxe2x80x9d is intended, unless expressly indicated otherwise, to mean groups containing no more than 7 carbon atoms, more often, no more than 4, frequently one or two carbon atoms.
The Hydrocarbon Polymer with Groups A and B
The hydrocarbon polymer onto which are attached the groups A and B is derived from (P) an olefinically unsaturated hydrocarbon polymer as described in greater detail hereinafter, and optionally, mixtures of the polymer (P) and olefinically unsaturated compounds having molecular weight ranging from about 100 to less than 20,000.
When mixtures are used, they typically comprise from about 1% by weight, often from about 5%, occasionally from about 10% up to about 50% by weight, often up to about 25% by weight of olefinically unsaturated compound having molecular weight ranging from about 100 to less than 20,000.
The polymer onto which groups A and B are attached may contain up to about 5% residual olefinic unsaturation, that is, up to about 5% of the carbon to carbon bonds may be olefinically unsaturated. Preferably, no more than about 1%, even more often no more than about 0.1% of the carbon to carbon bonds are unsaturated. Most preferably the polymer is substantially saturated, that is, all of the carbon to carbon bonds are saturated or only a minor, insignificant number of carbon to carbon bonds are olefinically unsaturated.
The extent of olefinic unsaturation which may remain in the hydrocarbon polymer after attachment of groups A and B may be adjusted by hydrogenation of some of the olefinic bonds present in (P) before reaction with a carboxylic reactant (G) as discussed in greater detail hereinafter. Alternatively, the intermediate arising from reaction of (P) and (G) may be hydrogenated, if desired to reduce or eliminate remaining unsaturation.
The groups A and B are attached to the hydrocarbon polymer as set forth in greater detail hereinbelow.
The Group A
The hydrocarbon polymer may have attached thereto one or more groups A which consist of
groups of the formula 
wherein R3 is H or hydrocarbyl, R4 is a divalent hydrocarbylene group, n=0 or 1, and each of R9 and R10 is independently H, alkoxyhydrocarbyl, hydroxyhydrocarbyl, hydrocarbyl, aminohydrocarbyl, N-alkoxyalkyl- or hydroxyalkyl-substituted aminohydrocarbyl, or a group of the formula "Parenopenst"Y"Parenclosest"cR11xe2x80x94M, wherein each Y is independently a group of the formula 
each R11 is a divalent hydrocarbyl group, R12 is as defined above for R9 and R10, and M is H, hydrocarbyl, amino, xe2x80x94OH, an amide group, an amide-containing group, an acylamino group, an imide group, a heterocyclic group, for example a morpholine group, a piperidine group, a piperazine group, a thiadiazole group, and other heterocyclic groups containing at least one ring S, N or O atom, an imide-containing group, or xe2x80x94SRxe2x80x2 wherein Rxe2x80x2 is H or hydrocarbyl, preferably H or lower alkyl, and c is 0 or a number ranging from 1 to about 100, or one of R9 and R10 taken together with the adjacent N constitute a Nxe2x80x94N group. Preferably, no more than three R9, R10, and R12 contain amide groups, imide-containing groups, acylamino groups or amide-containing groups.
R3 is H or hydrocarbyl. These hydrocarbyl groups are usually aliphatic, that is, alkyl or alkenyl, preferably alkyl, more preferably lower alkyl. Especially preferred is where R3 is H or methyl, most preferably, H.
R4 is a divalent hydrocarbylene group. This group may be aliphatic or aromatic, but is usually aliphatic. Often, R4 is an alkylene group containing from 1 to about 3 carbon atoms. The xe2x80x98nxe2x80x99 is 0 or 1; that is, in one embodiment R4 is present and in another embodiment, R4 is absent. More often, R4 is absent.
In one preferred embodiment, R3 is hydrogen or a lower alkyl or alkenyl group. In one especially preferred embodiment, R3 is hydrogen and n=0.
The subscript a denotes the number of A groups. The subscript a is 0 or ranges from 1 to about 50. When a=0, the group A is absent. Often, a ranges from 1 to about 10.
The Group B
The hydrocarbon polymer has attached thereto one or more groups B, each of which is independently selected from members of the group of formula: 
wherein each X is independently O, S, or NRb, each Rb is independently H, NH2, hydrocarbyl, hydroxy-hydrocarbyl or aminohydrocarbyl, and each Z is independently a group of the formula 
wherein
each of R3, R4, and n is as defined hereinabove;
Ra is an ethylene group, a propylene group, which groups optionally have hydrocarbyl or hydroxyhydrocarbyl substituents, or 
wherein J is H, SH, NH2, or OH, and tautomers thereof, the subscript b is a number ranging from 1 to about 30.
The compositions of this invention may be prepared by a process which comprises first reacting, optionally in the presence of an acid catalyst,
(P) an olefinically unsaturated hydrocarbon polymer having {overscore (M)}n ranging from 20,000 to about 500,000 when the polymer is not a star polymer, and up to about GPC peak molecular weight of 4,000,000 when the polymer is a star polymer, with
(G) from about 0.1 to about 3 moles per mole-equivalent of (P), often from about 0.8 moles to about 1.2 moles, more often from about 0.95 moles to about 1.05 moles per mole-equivalent of (P). of at least one carboxylic reactant selected from the group consisting of compounds of the formula
R3C(O)(R4)nC(O)OR5xe2x80x83xe2x80x83(IV)
wherein each of R3 and R5 is independently H or a hydrocarbyl group, R4 is a divalent hydrocarbylene group, and n is 0 or 1, and reactive sources thereof to form a carboxylic group containing intermediate, then reacting said intermediate with
(C) from about 0.5 to about 1.25 equivalents, per equivalent of carboxylic acid or reactive source thereof, of a heterocycle precursor.
The amount of (G) reacted per mole of (P) will depend, in part, on the amount of olefinic unsaturation present in (P). For use as an intermediate for further reaction with (C) to prepare dispersant-viscosity improver additives for lubricating oils, the amount of (G) reacted with (P) often will range from about 1 to about 100 moles (G) per mole of (P) wherein one mole of (P) is defined herein as the number average molecular weight of (P). Preferably, in this embodiment from about 2, often from about 5, up to about 50 moles (G), often up to about 20, frequently up to about 10 moles (G) are utilized per mole of (P).
The process of this invention comprising reacting (P) and (G) is conducted at temperatures ranging from ambient, usually from about 60xc2x0 C., often from about 100xc2x0 C., up to about 250xc2x0 C., more often up to about 180xc2x0 C., preferably up to about 160xc2x0 C.
The reaction with the heterocycle precursor is conducted at temperatures ranging from about 100xc2x0 C. to about 250xc2x0 C., preferably from about 120xc2x0 C. to about 180xc2x0 C., and occasionally from about 180xc2x0 C. to about 225xc2x0 C. for a sufficient time to convert at least about 50% of the carboxylic groups to heterocyclic groups.
One or both steps of the process may be conducted in the presence of a diluent, usually an oil of lubricating viscosity. Other diluents may be used; particularly if it is desired to remove the diluent before further use of the product. Such other diluents include relatively low boiling point liquids such as hydrocarbon solvents and the like.
The process may be conducted in a kettle type reactor. Under these conditions, it is frequently advantageous to utilize a diluent to improve processing. Alternatively, other reactors may be used. In one particular embodiment, the reactor is an extruder. Usually, processing in an extruder does not require the use of a diluent, although a diluent may be used if desired. It is not necessary that both steps of the process be conducted in the same type of reactor.
(P) The Olefinically Unsaturated Hydrocarbon Polymer
As used herein, the expression xe2x80x98polymerxe2x80x99 refers to polymers of all types, i.e., homopolymers and copolymers. The term homopolymer refers to polymers derived from essentially one monomeric species; copolymers are defined herein as being derived from 2 or more monomeric species.
The olefinically unsaturated hydrocarbon polymer is an essentially hydrocarbon based polymer, usually one having a number average molecular weight ({overscore (M)}n) between 20,000 and about 500,000, often from 20,000 to about 300,000. Molecular weights of the hydrocarbon polymer are determined using well known methods described in the literature. Examples of procedures for determining the molecular weights are gel permeation chromatography (GPC) (also known as size-exclusion chromatography) and vapor phase osmometry (VPO). These and other procedures are described in numerous publications including:
P. J. Flory, xe2x80x9cPrinciples of Polymer Chemistryxe2x80x9d, Cornell University Press (1953), Chapter VII, pp 266-316,
xe2x80x9cMacromolecules, an Introduction to Polymer Sciencexe2x80x9d, F. A. Bovey and F. H. Winslow, Editors, Academic Press (1979), pp 296-312, and
W. W. Yau, J. J. Kirkland and D. D. Bly, xe2x80x9cModern Size Exclusion Liquid Chromatographyxe2x80x9d, John Wiley and Sons, New York, 1979.
Unless otherwise indicated, GPC molecular weights referred to herein are polystyrene equivalent weights, i.e., are molecular weights determined employing polystyrene standards.
A measurement which is complementary to a polymer""s molecular weight is the melt index (ASTM D-1238). Polymers of high melt index generally have low molecular weight, and vice versa. The polymers of the present invention preferably have a melt index of up to 20 dg/min., more preferably 0.1 to 10 dg/min.
These publications are hereby incorporated by reference for relevant disclosures contained therein relating to the determination of molecular weight.
When the molecular weight of a polymer is greater than desired, it may be reduced by techniques known in the art. Such techniques include mechanical shearing of the polymer employing masticators, ball mills, roll mills, extruders and the like. Oxidative or thermal shearing or degrading techniques are also useful and are known. Details of numerous procedures for shearing polymers are given in U.S. Pat. No. 5,348,673 which is hereby incorporated herein by reference for relevant disclosures in this regard. Reducing molecular weight also tends to improve the subsequent shear stability of the polymer.
The polymer may contain aliphatic, aromatic or cycloaliphatic components, or mixtures thereof. When the polymer is prepared from the monomers, it may contain substantial amounts of olefinic unsaturation, oftentimes far in excess of that which is desired for this invention. The polymer may be subjected to hydrogenation to reduce the amount of unsaturation to such an extent that the resulting hydrogenated polymer has olefinic unsaturation, based on the total number of carbon to carbon bonds in the polymer, of less than 5%, frequently less than 2%, often no more than 1% olefinic unsaturation. As noted hereinabove, the hydrocarbon polymer is olefinically unsaturated. Accordingly, the polymer contains one or more olefinic double bonds. When the polymer is subjected to hydrogenation, it is not exhaustively hydrogenated.
Typically, from about 90 to about 99.9% of carbon to carbon bonds in the polymer are saturated.
Aromatic unsaturation is not considered olefinic unsaturation within the context of this invention. Depending on hydrogenation conditions, up to about 20% of aromatic groups may be hydrogenated; however, typically no more than about 5%, usually less than 1% of aromatic bonds are hydrogenated. Most often, substantially none of the aromatic bonds are hydrogenated.
Typically, (P) the olefinically unsaturated polymer contains an average of from 1 to about 9000 olefinic double bonds, more often from about 1 to about 100 olefinic double bonds, even more often from about 1, frequently 2 to about 10, up to about 50 olefinic double bonds per molecule based on the {overscore (M)}n of the polymer. In another embodiment, (P) contains about 1 olefinic double bond for about every 20, often for about every 70 to 7000 carbon atoms. In still another embodiment, the hydrocarbon polymer (P) contains about 1 olefinic double bond for every 4,000 to 20,000 on {overscore (M)}n basis, often, about 1 olefinic double bond per 1,000 to 40,000 on {overscore (M)}n basis. Thus, for example, in this embodiment a polymer of {overscore (M)}n=80,000 would contain from about 2 to about 80 olefinic double bonds per molecule, often from about 4 to about 20 double bonds per molecule. In yet another embodiment, the hydrocarbon polymer (P) contains about 1 olefinic double bond for about every 300 to 100,000 on {overscore (M)}n basis.
The equivalent weight per mole of carbon to carbon double bonds is defined herein as the mole-equivalent weight. For example, a polymer having {overscore (M)}n of 100,000 and which contains an average of 4 moles of carbon to carbon double bonds, has a mole equivalent weight of 100,000/4=25,000. Conversely, the polymer has one mole of carbon to carbon double bonds per 25,000 {overscore (M)}n.
In preferred embodiments, the hydrocarbon polymer is at least one oil soluble or dispersible homopolymer or copolymer selected from the group consisting of:
(1) polymers of dienes;
(2) copolymers of conjugated dienes with vinyl substituted aromatic compounds;
(3) polymers of aliphatic olefins having from 2 to about 28 carbon atoms;
(4) olefin-diene copolymers; and
(5) star polymers.
These preferred polymers are described in greater detail hereinbelow.
(1) Polymers of Dienes
The hydrocarbon polymer may be a homopolymer or copolymer of one or more dienes. The dienes may be conjugated such as isoprene, butadiene and piperylene or non-conjugated such as 1-4 hexadiene, ethylidene norbornene, vinyl norbornene, 4-vinyl cyclohexene, and dicyclopentadiene. Polymers of conjugated dienes are preferred. Such polymers are conveniently prepared via free radical and anionic polymerization techniques. Emulsion techniques are commonly employed for free radical polymerization.
As noted hereinabove, useful polymers have {overscore (M)}n ranging from 20,000 to about 500,000. More often, useful polymers of this type have {overscore (M)}n ranging from about 50,000 to about 150,000.
These polymers may be and often are hydrogenated to reduce the amount of olefinic unsaturation present in the polymer. They are not exhaustively hydrogenated.
Hydrogenation is often accomplished employing catalytic methods. Catalytic techniques employing hydrogen under high pressure and at elevated temperature are well-known to those skilled in the chemical art. Other methods are also usefull and are well known to those skilled in the art.
Extensive discussions of diene polymers appear in the xe2x80x9cEncyclopedia of Polymer Science and Engineeringxe2x80x9d, Volume 2, pp 550-586 and Volume 8, pp 499-532, Wiley-Interscience (1986), which are hereby expressly incorporated herein by reference for relevant disclosures in this regard.
The polymers include homopolymers and copolymers of conjugated dienes including polymers of 1,3-dienes of the formula 
wherein each substituent denoted by R, or R with a numerical subscript, is independently hydrogen or hydrocarbon based, wherein hydrocarbon based is as defined hereinabove. Preferably at least one substituent is H. Normally, the total carbon content of the diene will not exceed 20 carbons. Preferred dienes for preparation of the polymer are piperylene, isoprene, 2,3-dimethyl-1,3-butadiene, chloroprene and 1,3-butadiene.
Suitable homopolymers of conjugated dienes are described, and methods for their preparation are given in numerous U.S. patents, including the following:
U.S. Pat. No. 3,547,821
U.S. Pat. No. 3,835,053
U.S. Pat. No. 3,959,161
U.S. Pat. No. 3,965,019
U.S. Pat. No. 4,085,055
U.S. Pat. No. 4,116,917
As a specific example, U.S. Pat. No. 3,959,161 teaches the preparation of hydrogenated polybutadiene. In another example, upon hydrogenation, 1,4-polyisoprene becomes an alternating copolymer of ethylene and propylene.
Copolymers of conjugated dienes are prepared from two or more conjugated dienes. Useful dienes are the same as those described in the preparation of homopolymers of conjugated dienes hereinabove. The following U.S. Patents describe diene copolymers and methods for preparing them:
U.S. Pat. No. 3,965,019
U.S. Pat. No. 4,073,737
U.S. Pat. No. 4,085,055
U.S. Pat. No. 4,116,917
For example, U.S. Pat. No. 4,073,737 describes the preparation and hydrogenation of butadiene-isoprene copolymers.
(2) Copolymers of Conjugated Dienes with Vinyl Substituted Aromatic Compounds
In one embodiment, the hydrocarbon polymer is a copolymer of a vinyl-substituted aromatic compound and a conjugated diene. The vinyl substituted aromatics generally contain from 8 to about 20 carbons, preferably from 8 to 12 carbon atoms and most preferably, 8 or 9 carbon atoms.
These polymers may be, and often are, hydrogenated to reduce the amount of olefinic unsaturation present in the polymer. They are not exhaustively hydrogenated.
Examples of vinyl substituted aromatics include vinyl anthracenes, vinyl naphthalenes and vinyl benzenes (styrenic compounds). Styrenic compounds are preferred, examples being styrene, alpha-methystyrene, ortho-methyl styrene, meta-methyl styrene, para-methyl styrene, para-tertiary-butylstyrene, and chlorostyrene with styrene being preferred.
The conjugated dienes generally have from 4 to about 10 carbon atoms and preferably from 4 to 6 carbon atoms. Example of conjugated dienes include piperylene, 2,3-dimethyl-1,3-butadiene, chloroprene, isoprene and 1,3-butadiene, with isoprene and 1,3-butadiene being particularly preferred. Mixtures of such conjugated dienes are useful.
The vinyl substituted aromatic content of these copolymers is typically in the range of about 20% to about 70% by weight, preferably about 40% to about 60% by weight. The aliphatic conjugated diene content of these copolymers is typically in the range of about 30% to about 80% by weight, preferably about 40% to about 60% by weight.
The polymers, and in particular, styrene-diene copolymers, can be random copolymers or block copolymers, which include regular block copolymers or random block copolymers. Random copolymers are those in which the comonomers are randomly, or nearly randomly, arranged in the polymer chain with no significant blocking of homopolymer of either monomer. Regular block copolymers are those in which a small number of relatively long chains of homopolymer of one type of monomer are alternately joined to a small number of relatively long chains of homopolymer of another type of monomer. Random block copolymers are those in which a larger number of relatively short segments of homopolymer of one type of monomer alternate with relatively short segments of homopolymer of another monomer.
The random, regular block and random block polymers used in this invention may be linear, or they may be partially or highly branched. The relative arrangement of homopolymer segments in a linear regular block or random block polymer is obvious. Differences in structure lie in the number and relative sizes of the homopolymer segments; the arrangement in a linear block polymer of either type is always alternating in homopolymer segments.
Normal or regular block copolymers usually have from 1 to about 5, often 1 to about 3, preferably only from 1 to about 2 relatively large homopolymer blocks of each monomer. Thus, a linear regular diblock copolymer of styrene or other vinyl aromatic monomer (S) and diene (D) would have a general structure represented by a large block of homopolymer (S) attached to a large block of homopolymer (D), as:
(S)s(D)d
where subscripts s and d are as described hereinbelow. Similarly, a regular linear tri-block copolymer of styrene or other vinyl aromatic monomer (S) and diene monomer (D) may be represented, for example, by (S)s(D)d(S)s or (D)d(S)s(D)d. Techniques vary for the preparation of these xe2x80x9cSxe2x80x94Dxe2x80x94Sxe2x80x9d and xe2x80x9cDxe2x80x94Sxe2x80x94Dxe2x80x9d triblock polymers, and are described in the literature for anionic polymerization.
A third monomer (T) may be incorporated into linear, regular block copolymers. Several configurations are possible depending on how the homopolymer segments are arranged with respect to each other. For example, linear triblock copolymers of monomers (S), (D) and (T) can be represented by the general configurations:
(S)sxe2x80x94(D)dxe2x80x94(T)t, (S)sxe2x80x94(T)txe2x80x94(D)d, or (D)dxe2x80x94(S)sxe2x80x94(T)t,
wherein the lower case letters s, d and t represent the approximate number of monomer units in the indicated block.
The sizes of the blocks are not necessarily the same, but may vary considerably. The only stipulation is that any regular block copolymer comprises relatively few, but relatively large, alternating homopolymer segments.
As an example, when (D) represents blocks derived from diene such as isoprene or butadiene, xe2x80x9cdxe2x80x9d usually ranges from about 100 to about 2000, preferably from about 500 to about 1500; when (S) represents, for example, blocks derived from styrene, xe2x80x9csxe2x80x9d usually ranges from about 100 to about 2000, preferably from about 200 to about 1000; and when a third block (T) is present, xe2x80x9ctxe2x80x9d usually ranges from about 10 to about 1000, provided that the {overscore (M)}n of the polymer is within the ranges indicated as useful for this invention.
The copolymers can be prepared by methods well known in the art. Such copolymers usually are prepared by anionic polymerization using Group Ia metals in the presence of electron-acceptor aromatics, or preformed organometallics such as sec-butyllithium as polymerization catalysts.
The styrene/diene block polymers are usually made by anionic polymerization, using a variety of techniques, and altering reaction conditions to produce the most desirable features in the resulting polymer. In an anionic polymerization, the initiator can be either an organometallic material such as an alkyl lithium, or the anion formed by electron transfer from a Group Ia metal to an aromatic material such as naphthalene. A preferred organometallic material is an alkyl lithium such as sec-butyl lithium; the polymerization is initiated by addition of the butyl anion to either the diene monomer or to the styrene.
When an alkyl lithium initiator is used, a homopolymer of one monomer, e.g., styrene, can be selectively prepared, with each polymer molecule having an anionic terminus, and lithium gegenion. The carbanionic terminus remains an active initiation site toward additional monomers. The resulting polymers, when monomer is completely depleted, will usually all be of similar molecular weight and composition, and the polymer product will be xe2x80x9cmonodispersexe2x80x9d (i.e., the ratio of weight average molecular weight to number average molecular weight is very nearly 1.0). At this point, addition of 1,3-butadiene, isoprene or other suitable anionically polymerizable monomer to the homopolystyrene-lithium xe2x80x9clivingxe2x80x9d polymer produces a second segment which grows from the terminal anion site to produce a living di-block polymer having an anionic terminus, with lithium gegenion.
Subsequent introduction of additional styrene can produce a new poly S-block-poly D-block-poly S, or Sxe2x80x94Dxe2x80x94S triblock polymer; higher orders of block polymers can be made by consecutive stepwise additions of different monomers in different sequences.
Alternatively, a living diblock polymer can be coupled by exposure to an agent such as a dialkyl dichlorosilane. When the carbanionic xe2x80x9cheadsxe2x80x9d of two Sxe2x80x94D diblock living polymers are coupled using such an agent, precipitation of LiCl occurs to give an Sxe2x80x94Dxe2x80x94S triblock polymer.
Block copolymers made by consecutive addition of styrene to give a relatively large homopolymer segment (S), followed by a diene to give a relatively large homopolymer segment (D), are referred to as poly-S-block-poly-D copolymers, or Sxe2x80x94D diblock polymers.
When metal naphthalide is employed as initiator, the dianion formed by electron transfer from metal, e.g., Na, atoms to the naphthalene ring can generate dianions which may initiate polymerization, e.g. of monomer S, in two directions simultaneously, producing essentially a homopolymer of S having anionic termini at both ends.
Subsequent exposure of the poly (S) dianion to a second monomer (D) results in formation of a poly D-block-poly S-block-poly D, or a Dxe2x80x94Sxe2x80x94D triblock polymeric dianion, which may continue to interact with additional anionically-polymerizable monomers of the same, or different chemical type, in the formation of higher order block polymers. Ordinary block copolymers are generally considered to have up to about 5 such blocks.
Usually, one monomer or another in a mixture will polymerize faster, leading to a segment that is richer in that monomer, interrupted by occasional incorporation of the other monomer. This can be used to build a type of polymer referred to as a xe2x80x9crandom block polymerxe2x80x9d, or xe2x80x9ctapered block polymerxe2x80x9d. When a mixture of two different monomers is anionically polymerized in a non-polar paraffinic solvent, one will initiate selectively, and usually polymerize to produce a relatively short segment of homopolymer. Incorporation of the second monomer is inevitable, and this produces a short segment of different structure. Incorporation of the first monomer type then produces another short segment of that homopolymer, and the process continues, to give a xe2x80x9crandomxe2x80x9d alternating distribution of relatively short segments of homopolymers, of different lengths. Random block polymers are generally considered to be those comprising more than 5 such blocks. At some point, one monomer will become depleted, favoring incorporation of the other, leading to ever longer blocks of homopolymer, resulting in a xe2x80x9ctapered block copolymer.xe2x80x9d
An alternative way of preparing random or tapered block copolymers involves initiation of styrene, and interrupting with periodic, or step, additions of diene monomer. The additions are programmed according to the relative reactivity ratios and rate constants of the styrene and particular diene monomer.
xe2x80x9cPromotersxe2x80x9d are electron-rich molecules that facilitate anionic initiation and polymerization rates while lessening the relative differences in rates between various monomers. Promoters also influence the way in which diene monomers are incorporated into the block polymer, favoring 1,2-polymerization of dienes over the normal 1,4-cis-addition.
These polymers may have considerable olefinic unsaturation, which may be reduced, if desired. Hydrogenation to reduce the extent of olefinic unsaturation may be carried out to reduce approximately 90-99.1% of the olefinic unsaturation of the initial polymer, such that from about 90 to about 99.9% of the carbon to carbon bonds of the polymer are saturated. In general, it is preferred that these copolymers contain no more than about 10%, preferably no more than 5% and often no more than about 0.5% residual olefinic unsaturation on the basis of the total amount of olefinic double bonds present in the polymer prior to hydrogenation. As noted above, the polymers are olefinically unsaturated; accordingly, the polymers are not exhaustively hydrogenated. Unsaturation can be measured by a number of means well known to those of skill in the art, including infrared, nuclear magnetic resonance spectroscopy, bromine number, iodine number, and other means. Aromatic unsaturation is not considered to be olefinic unsaturation within the context of this invention.
Hydrogenation techniques are well known to those of skill in the art. One common method is to contact the copolymers with hydrogen, often at superatmospheric pressure in the presence of a metal catalyst such as colloidal nickel, palladium supported on charcoal, etc. Hydrogenation may be carried out as part of the overall production process, using finely divided, or supported, nickel catalyst. Other transition metals may also be used to effect the transformation. Other techniques are known in the art.
Other polymerization techniques such as emulsion polymerization can be used.
Often the arrangement of the various homopolymer blocks is dictated by the reaction conditions such as catalyst and polymerization characteristics of the monomers employed. Conditions for modifying arrangement of polymer blocks are well known to those of skill in the polymer art. Literature references relating to polymerization techniques and methods for preparing certain types of block polymers include:
1) xe2x80x9cEncyclopedia of Polymer Science and Engineeringxe2x80x9d, Wiley-Interscience Publishing, New York, (1986);
2) A. Noshay and J. E. McGrath, xe2x80x9cBlock Copolymersxe2x80x9d, Academic Press, New York, (1977);
3) R. J. Ceresa, ed., xe2x80x9cBlock and Graft Copolymerizationxe2x80x9d, John Wiley and Sons, New York, (1976); and
4) D. J. Meier, ed., (Block Copolymersxe2x80x9d, MMI Press, Harwood Academic Publishers, New York, (1979).
Each of these is hereby incorporated herein by reference for relevant disclosures relating to block copolymers.
Examples of suitable commercially available regular linear diblock copolymers as set forth above include Shellvis-40, and Shellvis-50, both hydrogenated styrene-isoprene block copolymers, manufactured by Shell Chemical.
Examples of commercially available random block and tapered block copolymers include the various Glissoviscal styrene-butadiene copolymers manufactured by BASF. A previously available random block copolymer was Phil-Ad viscosity improver, manufactured by Phillips Petroleum.
The copolymers preferably have {overscore (M)}n in the range of 20,000 to about 500,000, more preferably from about 30,000 to about 150,000. The weight average molecular weight ({overscore (M)}w) for these copolymers is generally in the range of about 50,000 to about 500,000, preferably from about 50,000 to about 300,000.
Copolymers of conjugated dienes with olefins containing aromatic groups, e.g., styrene, methyl styrene, etc. are described in numerous patents including the following:
For example, U.S. Pat. No. 3,554,91 describes a random butadiene-styrene copolymer, its preparation and hydrogenation.
(3) Polymers of Aliphatic Olefins
Another useful hydrocarbon polymer is one which in its main chain is composed essentially of aliphatic olefin, especially alpha olefin, monomers. The polyolefins of this embodiment thus exclude polymers which have a large component of other types of monomers copolymerized in the main polymer, such as ester monomers, acid monomers, and the like. The polyolefin may contain impurity amounts of such materials, e.g., less than 5% by weight, more often less than 1% by weight, preferably, less than 0.1% by weight of other monomers. Useful polymers include oil soluble or dispersible polymers of alpha-olefins.
The olefin copolymer preferably has a number average molecular weight ({overscore (M)}n) determined by gel-permeation chromatography employing polystyrene standards, ranging from 20,000 to about 500,000, often from about 30,000 to about 300,000, often to about 200,000, more often from about 50,000 to about 150,000, even more often from about 80,000 to about 150,000. Exemplary polydispersity values ({overscore (M)}w/{overscore (M)}n) range from about 1.5 to about 3.5, often to about 3.0, preferably, from about 1.7, often from about 2.0, to about 2.5.
These polymers are preferably polymers of alpha-olefins having from 2 to about 28 carbon atoms. Preferably they are copolymers, more preferably copolymers of ethylene and at least one other xcex1-olefin having from 3 to about 28 carbon atoms, i.e., one of the formula CH2xe2x95x90CHR1 wherein R1 is straight chain or branched chain alkyl radical comprising 1 to 26 carbon atoms. Examples include monoolefins such as propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. Preferably R1 in the above formula is alkyl of from 1 to 8 carbon atoms, and more preferably is alkyl of from 1 to 2 carbon atoms. Preferably, the polymer of olefins is an ethylene-propylene copolymer.
The ethylene content is preferably in the range of 20 to 80 percent by weight, and more preferably 30 to 70 percent by weight. When propylene and/or 1-butene are employed as comonomer(s) with ethylene, the ethylene content of such copolymers is most preferably 45 to 65 percent, although higher or lower ethylene contents may be present. Most preferably, these polymers are substantially free of ethylene homopolymer, although they may exhibit a degree of crystallinity due to the presence of small crystalline polyethylene segments within their microstructure.
In one particular embodiment, the polymer is a homopolymer derived from a butene, particularly, isobutylene. Especially preferred is where the polymer comprises terminal vinylidene olefinic double bonds.
The polymers employed in this embodiment may generally be prepared substantially in accordance with procedures which are well known in the art.
Catalysts employed in the production of the reactant polymers are likewise well known. One broad class of catalysts particularly suitable for polymerization of xcex1-olefins, comprises coordination catalysts such as Ziegler or Ziegler-Natta catalysts comprising a transition metal atom. Ziegler-Natta catalysts are composed of a combination of a transition metal atom with an organo aluminum halide and may be used with additional complexing agents.
Other useful polymerization catalysts are the metallocene compounds. These are organometallic coordination compounds obtained as cyclopentadienyl derivatives of a transition metal or metal halide. The metal is bonded to the cyclopentadienyl ring by electrons moving in orbitals extending above and below the plane of the ring (xcfx80 bond). The use of such materials as catalysts for the preparation of ethylene-alpha olefin copolymers is described in U.S. Pat. No. 5,446,221. The procedure described therein provides ethylene-alpha olefin copolymers having at least 30% of terminal ethenylidene unsaturation. This patent is hereby incorporated herein by reference for relevant disclosures.
Polymerization using coordination catalysis is generally conducted at temperatures ranging between 20xc2x0 and 300xc2x0 C., preferably between 30xc2x0 and 200xc2x0 C. Reaction time is not critical and may vary from several hours or more to several minutes or less, depending upon factors such as reaction temperature, the monomers to be copolymerized, and the like. One of ordinary skill in the art may readily obtain the optimum reaction time for a given set of reaction parameters by routine experimentation. Preferably, the polymerization will generally be completed at a pressure of 1 to 40 MPa (10 to 400 bar).
The polymerization may be conducted employing liquid monomer, such as liquid propylene, or mixtures of liquid monomers (such as mixtures of liquid propylene and 1-butene), as the reaction medium. Alternatively, polymerization may be accomplished in the presence of a hydrocarbon inert to the polymerization such as butane, pentane, isopentane, hexane, isooctane, decane, toluene, xylene, and the like.
When carrying out the polymerization in a batch-type fashion, the reaction diluent (if any) and the alpha-olefin comonomer(s) are charged at appropriate ratios to a suitable reactor. Care should be taken that all ingredients are dry, with the reactants typically being passed through molecular sieves or other drying means prior to their introduction into the reactor. Subsequently, component(s) of the catalyst are introduced while agitating the reaction mixture, thereby causing polymerization to commence. Alternatively, component(s) of the catalyst may be premixed in a solvent and then fed to the reactor. As polymer is being formed, additional monomers may be added to the reactor. Upon completion of the reaction, unreacted monomer and solvent are either flashed or distilled off, if necessary by vacuum, and the copolymer withdrawn from the reactor.
The polymerization may be conducted in a continuous manner by simultaneously feeding the reaction diluent (if employed), monomers, component(s) of the catalyst to a reactor and withdrawing solvent, unreacted monomer and polymer from the reactor so as to allow a residence time of ingredients long enough for forming polymer of the desired molecular weight; and separating the polymer from the reaction mixture.
In those situations wherein the molecular weight of the polymer product that would be produced at a given set of operating conditions is higher than desired, any of the techniques known in the prior art for control of molecular weight, such as polymerization temperature control, may be used.
The polymers are preferably formed in the substantial absence of added H2 gas, that is H2 gas added in amounts effective to substantially reduce the polymer molecular weight.
The polymers can be random copolymers, block copolymers, and random block copolymers. Ethylene propylene copolymers are usually random copolymers. Block copolymers may be obtained by conducting the reaction in a tubular reactor. Such a procedure is described in U.S. Pat. No. 4,804,794 which is hereby incorporated by reference for relevant disclosures in this regard. Numerous United States patents, including the following, describe the preparation of copolymers of alpha olefins.
Copolymers of ethylene with higher alpha olefins are the most common copolymers of aliphatic olefins. Ethylene-propylene copolymers are the most common ethylene-alpha-olefin copolymers and are preferred for use in this invention. A description of an ethylene-propylene copolymer appears in U.S. Pat. No. 4,137,185 which is hereby incorporated herein by reference.
Useful ethylene-alpha olefin, usually ethylene-propylene, copolymers are commercially available from numerous sources including the Exxon, Texaco and Lubrizol Corporations.
(4) Olefin-Diene Copolymers
Another useful hydrocarbon polymer is one derived from olefins, especially lower olefins, and dienes. Preferred olefins are alpha olefins. Dienes may be non-conjugated or conjugated, usually non-conjugated. Useful olefins and dienes are the same as those described hereinabove and hereinafter in discussions of other polymer types.
In one embodiment, the copolymer is an ethylene-lower olefin-diene copolymer. As used herein, the term lower refers to groups or compounds containing no more than 7 carbon atoms. Preferably, the diene is non-conjugated. Especially preferred are ethylene-propylene-diene copolymers.
These copolymers most often will have {overscore (M)}n ranging from 20,000 to about 500,000, preferably from about 50,000 to about 200.000. In another embodiment, the {overscore (M)}n ranges from about 70,000 to about 350,000. These polymers often have a relatively narrow range of molecular weight as represented by the polydispersity value {overscore (M)}w/{overscore (M)}n. Typically, the polydispersity values are less than 10, more often less than 6, and preferably less than 4, often between 2 and 3.
There are numerous commercial sources for lower olefin-diene copolymers. For example, Ortholeum(copyright) 2052 (a product marketed by the DuPont Company) which is a terpolymer having an ethylene:propylene weight ratio of about 57:43 and containing 4-5 weight % of groups derived from 1,4-hexadiene monomer. Other commercially available olefin-diene copolymers including ethylene-propylene copolymers with ethylidene norbornene, with dicyclopentadiene, with vinyl norbornene, with 4-vinyl cyclohexene, and numerous other such materials are readily available. Olefin-diene copolymers and methods for their preparation are described in numerous patents including the following U.S. Patents:
U.S. Pat. No. 3,291,780
U.S. Pat. No. 3,300,459
U.S. Pat. No. 3,598,738
U.S. Pat. No. 4,026,809
U.S. Pat. No. 4,032,700
U.S. Pat. No. 4,156,061
U.S. Pat. No. 3,320,019
U.S. Pat. No. 4,357,250
U.S. Pat. No. 3,598,738, which describes the preparation of ethylene-propylene-1,4-hexadiene terpolymers, is illustrative. This patent also lists numerous references describing the use of various polymerization catalysts.
Another useful polymer is an olefin-conjugated diene copolymer. An example of such a polymer is butyl rubber, an isobutylene-isoprene copolymer.
Details of various types of polymers, reaction conditions, physical properties, and the like are provided in the above patents and in numerous books, including:
xe2x80x9cRiegel""s Handbook of Industrial Chemistryxe2x80x9d, 7th edition, James A. Kent Ed., Van Nostrand Reinhold Co., New York (1974), Chapters 9 and 10,
P. J. Flory, xe2x80x9cPrinciples of Polymer Chemistryxe2x80x9d, Cornell University Press, Ithaca, N.Y. (1953),
xe2x80x9cKirk-Othmer Encyclopedia of Chemical Technologyxe2x80x9d, 3rd edition, Vol. 8 (Elastomers, Synthetic, and various subheadings thereunder), John Wiley and Sons, New York (1979).
Each of the above-mentioned books and patents is hereby expressly incorporated herein by reference for relevant disclosures contained therein.
Polymerization can also be effected using free radical initiators in a well-known process, generally employing higher pressures than used with coordination catalysts. These polymers may be and frequently are hydrogenated to bring unsaturation to desired levels. As noted, hydrogenation may take place before or after reaction with the carboxylic reactant.
(5) Star Polymer
Star polymers are polymers comprising a nucleus and polymeric arms. Common nuclei include polyalkenyl compounds, usually compounds having at least two non-conjugated alkenyl groups, usually groups attached to electron withdrawing groups, e.g., aromatic nuclei. The polymeric arms are often homopolymers and copolymers of dienes, preferably conjugated dienes, vinyl substituted aromatic compounds such as monoalkenyl arenes, homopolymers of olefins such as butenes, especially isobutene, and mixtures thereof.
Molecular weights (GPC peak) of useful star polymers range from 20,000 to about 4 million. They frequently have {overscore (M)}n ranging from about 100,000 to about 2 million.
The polymers thus comprise a poly(polyalkenyl coupling agent) nucleus with polymeric arms extending outward therefrom. The star polymers are usually hydrogenated such that at least 80% of the olefinic carbon-carbon bonds are saturated, more often at least 90% and even more preferably, at least 95% are saturated. As noted herein, the polymers contain olefinic unsaturation; accordingly, they are not exhaustively saturated before reaction with the carboxylic reactant.
The polyvinyl compounds making up the nucleus are illustrated by polyalkenyl arenes, e.g., divinyl benzene and poly vinyl aliphatic compounds.
Dienes making up the polymeric arms are illustrated by butadiene, isoprene and the like. Monoalkenyl compounds include, for example, styrene and alkylated derivatives thereof. In one embodiment, the arms are derived from dienes. In another embodiment, the arms are derived from dienes and vinyl substituted aromatic compounds. In yet another embodiment, the arms comprise polyisobutylene groups. Arms derived from dienes or from dienes and vinyl substituted aromatic compounds are frequently substantially hydrogenated, provided that they are not exhaustively hydrogenated before reaction with the carboxylic reactant.
Star polymers are well known in the art. Such material and methods for preparing same are described in numerous publications and patents, including the following United States patents which are hereby incorporated herein by reference for relevant disclosures contained therein:
U.S. Pat. No. 4,116,917,
U.S. Pat. No. 4,141,847,
U.S. Pat. No. 4,346,193,
U.S. Pat. No. 4,358,565, and
U.S. Pat. No. 4,409,120.
Star polymers are commercially available, for example as Shellvis 200 sold by Shell Chemical Co.
Mixtures of two or more olefinically unsaturated hydrocarbon polymers may be used.
In another embodiment, mixtures of one or more of the olefinically unsaturated hydrocarbon polymers (P) with one or more olefins, other than the olefinically unsaturated hydrocarbon polymers identified as reactant (P) of this invention, may be used. Such a mixture comprises from about 0.1 mole equivalent of carbon to carbon double bonds to about 2 moles of an olefinically unsaturated compound having molecular weight ranging from about 100 to less than 20,000, often up to about 10,000 per mole equivalent of carbon to carbon double bonds in (P) the olefinically unsaturated polymer.
Examples include mixtures of any of the hydrocarbon polymers (P) with lower olefins, such as alpha-olefins containing up to about 100 carbon atoms, polyolefins, for example polyisobutylene, especially high vinylidene polyisobutylene, having molecular weights ranging from about 500 up to about 5,000, ethylene-propylene-diene compounds such as those identified by the tradename Trilene(copyright) and marketed by Uniroyal Chemical Co., and others.
(G) The Carboxylic Reactant
The carboxylic reactant is at least one member selected from the group consisting of compounds of the formula
R3C(O)(R4)nC(O)OR5xe2x80x83xe2x80x83(IV)
wherein each of R3 and R5 is independently H or a hydrocarbyl group, preferably H or lower alkyl, R4 is a divalent hydrocarbylene group, and n is 0 or 1, and reactive sources thereof Most preferably R3 is H
Reactive sources include compounds of the formula 
wherein each of R3 and R5 and each R9 is independently H or a hydrocarbyl group, R4 is a divalent hydrocarbylene group, and n is 0 or 1. These include acetals, ketals, hemiacetals and hemiketals of (IV) and esters thereof. Highly preferred are the compounds wherein one of R9 is hydrocarbyl and one is H: 
wherein each of R3 and R5 is independently H or a hydrocarbyl group, especially wherein the hydrocarbyl group is lower alkyl. R4 is a divalent hydrocarbylene group, preferably lower alkylene, R9 is hydrocarbyl, preferably lower alkyl, and n is 0 or 1, preferably 0. Especially preferred are the glyoxylate lower alkyl ester, lower alkyl hemiacetals. Cyclic trimers are useful.
Reactant (G) may be a compound of the formula 
wherein each of R3 and R5 is independently H or alkyl. Such compounds may arise when the carboxylic acid or ester reactant is hydrated.
R3 is usually H or an aliphatic group, that is, alkyl or alkenyl, preferably alkyl, more preferably lower alkyl. Especially preferred is where R3 is H or methyl, most preferably, H.
R4 is a divalent hydrocarbylene group. This group may be aliphatic or aromatic, but is usually aliphatic. Often, R4 is an alkylene group containing from 1 to about 3 carbon atoms. The xe2x80x98nxe2x80x99 is 0 or 1; that is, in one embodiment R4 is present and in another embodiment, R4 is absent. More often, R4 is absent.
When R5 is hydrocarbyl, it is usually an aliphatic group, often a group containing from 1 to about 30 carbon atoms, often from 8 to about 18 carbon atoms. In another embodiment, R5 is lower alkyl, wherein xe2x80x9clower alkylxe2x80x9d is defined hereinabove. Most often, R5 is H or lower alkyl, especially methyl, ethyl, propyl and butyl.
Examples of carboxylic reactants (G) are glyoxylic acid, and other omega-oxoalkanoic acids, glyoxylic acid hydrate, keto alkanoic acids such as pyruvic acid, levulinic acid, ketovaleric acids, ketobutyric acids, esters thereof, preferably the lower alkyl esters, methyl glyoxylate methyl hemiacetal, 4-formylbenzoic acid, 4-formylphenoxyacetic acid, esters thereof, carboxy benzaldehyde, the hemiacetals and hemiketals of keto- or aldehydoalkanoic acids such as glyoxylic acid and keto alkanoic acids such as pyruvic acid, levulinic acid, ketovaleric acids, and ketobutyric acids, and the corresponding acetals and ketals, and numerous others. The skilled worker, having the disclosure before him, will readily recognize the appropriate carboxylic reactant (B) to employ to generate a given intermediate. Preferred carboxylic reactants are those that will lead to preferred products of this invention.
In a preferred embodiment, R3 and one R9 are hydrogen and the other R9 and R5 are methyl. In this preferred embodiment, the reactant is represented by the structure 
and known as glyoxylic acid methylester methylhemiacetal. It is marketed by DSM Fine Chemicals.
The Catalyst
The first step of the process of this invention is optionally conducted in the presence of an acidic catalyst. Acid catalysts, such as organic sulfonic acids, for example, para-toluene sulfonic acid and methane sulfonic acid, heteropolyacids, the complex acids of heavy metals (e.g., Mo, W, Sn, V, Zr, etc.) with phosphoric acids (e.g., phosphomolybdic acid), and mineral acids, for example, H2SO4 and phosphoric acid, are useful. Solid acidic catalysts are useful. These include materials such as acidic clays, for example H2SO4 treated diatomaceous earth supplied under the name Super Filtrol, and polymer-bound acids such as those supplied under the name Amberlyst. Among useful solid catalysts are acidic oxides such as H2SO4 treated TiO2 and Al2O3. The amount of catalyst used is generally small, ranging from about 0.01 mole % to about 10 mole %, more often from about 0.1 mole % to about 2 mole %, based on moles of olefinic reactant.
(C) The Heterocycle Precursor
The compositions of this invention may be prepared by reacting the carboxylic group containing intermediate with a heterocycle precursor. These reactions generate the group xe2x80x98Bxe2x80x99 in the composition of formula (I). The heterocycle precursor is usually an acyclic reactant that cyclizes with the carboxylic group to form a heterocyclic compound. Materials which are useful as heterocycle precursors are compounds having the general formula
Hxe2x80x94W-alkylene-NH2xe2x80x83xe2x80x83(II)
wherein each W is selected from O, S, and NRb, the xe2x80x98alkylenexe2x80x99 group contains from 1 to about 8 carbon atoms. Preferably from about 2 to about 4 carbon atoms, and most preferably about 2, which carbon atoms may have one or more substituents selected from the group consisting of hydrocarbyl, hydroxyhydrocarbyl, and aminohydrocarbyl, wherein Rb is H, hydrocarbyl, hydroxyhydrocarbyl, or aminohydrocarbyl, and the general formula 
or salts thereof, wherein V is H2Nxe2x80x94 or H2NNHxe2x80x94, and U is O, S or NH.
Illustrative of suitable reactants (II) are alkanolamines, mercaptoalkylene amines, and di- and polyamines. Specific examples include ethanolamine, 2-aminopropanol, 2-methyl-2-amino-propanol, tris(hydroxymethyl) aminomethane, 2-mercaptoethylamine, ethylene diamine, 1-amino-2-methylaminoethane, diethylenetriamine, triethylene tetramine, and analogous ethylene polyamines including amine bottoms and condensed amines such as those described hereinbelow, alkoxylated ethylene polyamines such as N-(2-hydroxyethyl) ethylene diamine, and others.
Alkylene polyamines, especially ethylene polyamines, such as some of those mentioned above, are preferred. They are described in detail under the heading xe2x80x9cDiamines and Higher Aminesxe2x80x9d in Kirk Othmer""s xe2x80x9cEncyclopedia of Chemical Technologyxe2x80x9d, 4th Edition, Vol. 8, pages 74-108, John Wiley and Sons, New York (1993) and in Meinhardt, et al, U.S. Pat. No. 4,234,435, both of which are hereby incorporated herein by reference for disclosure of useful polyamines. Such polyamines are conveniently prepared by the reaction of ethylene dichloride with ammonia or by reaction of an ethylene imine with a ring opening reagent such as water, ammonia, etc. These reactions result in the production of a complex mixture of polyalkylene polyamines including cyclic condensation products. The mixtures are particularly useful.
Other useful types of polyamine mixtures are those resulting from stripping of the above-described polyamine mixtures removing lower molecular weight polyamines and volatile components to leave as residue what is often termed xe2x80x9cpolyamine bottomsxe2x80x9d. In general, alkylene polyamine bottoms can be characterized as having less than 2%, usually less than 1% (by weight) material boiling below about 200xc2x0 C. In the instance of ethylene polyamine bottoms, which are readily available and found to be quite useful, the bottoms contain less than about 2% (by weight) total diethylene triamine (DETA) or triethylene tetramine (TETA). A typical sample of such ethylene polyamine bottoms obtained from the Dow Chemical Company of Freeport, Texas, designated xe2x80x9cE-100xe2x80x9d has a specific gravity at 15.6xc2x0 C. of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40xc2x0 C. of 121 centistokes. Gas chromatography analysis of such a sample showed it contains about 0.93% xe2x80x9cLight Endsxe2x80x9d (most probably diethylenetriamine), 0.72% triethylenetetramine, 21.74% tetraethylene pentamine and 76.61% pentaethylene hexamine and higher (by weight). These alkylene polyamine bottoms include cyclic condensation products such as piperazine and higher analogs of diethylenetriamine, triethylenetetramine and the like.
In another embodiment, the polyamines are hydroxy-containing polyamines provided that the polyamine contains at least one condensable xe2x80x94Nxe2x80x94H group. Hydroxy-containing polyamine analogs of hydroxy monoamines, particularly alkoxylated alkylenepolyamines can also be used. Typically, the hydroxyamines are primary or secondary alkanol amines or mixtures thereof. Such amines can be represented by mono- and poly-N-hydroxyalkyl substituted alkylene polyamines wherein the alkylene polyamines are as described hereinabove; especially those that contain two to three carbon atoms in the alkylene radicals and the alkylene polyamine contains up to seven amino groups. Such polyamines can be made by reacting the above-described alkylene amines with one or more alkylene oxides. Conditions for carrying out such reactions are known to those skilled in the art.
Another useful polyamine is a condensation product obtained by reaction of at least one hydroxy compound with at least one polyamine reactant containing at least one primary or secondary amino group. These condensation products are characterized as being a polyamine product having at least one condensable primary or secondary amino group, made by contacting at least one hydroxy-containing material (b-i) having the general formula
(R)nYzxe2x80x94Xpxe2x80x94(A(OH)q)mxe2x80x83xe2x80x83(I)
wherein each R is independently H or a hydrocarbon based group, Y is selected from the group consisting of O, N, and S, X is a polyvalent hydrocarbon based group, A is a polyvalent hydrocarbon based group, n is 1 or 2, z is 0 or 1, p is 0 or 1, q ranges from 1 to about 10, and m is a number ranging from 1 to about 10; with (b-ii) at least one amine having at least one Nxe2x80x94H group.
The hydroxy material (b-i) can be any hydroxy material that will condense with the amine reactants (b-ii). These hydroxy materials can be aliphatic, cycloaliphatic, or aromatic; monools and polyols. Aliphatic compounds are preferred, and polyols are especially preferred. Highly preferred are aminoalcohols, especially those containing more than one hydroxyl group. Typically, the hydroxy-containing material (b-i) contains from 1 to about 10 hydroxy groups.
The hydroxy compounds are preferably polyhydric alcohols and amines, preferably polyhydric amines. Polyhydric amines include any of the above-described monoamines reacted with an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) having two to about 20 carbon atoms, preferably 2 to about 4. Examples of polyhydric amines include tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane, 2-amino-2-methyl-1,3-propanediol, N,N,Nxe2x80x2,Nxe2x80x2-tetrakis(2-hydroxypropyl) ethylenediamine, and N,N,Nxe2x80x2,Nxe2x80x2-tetrakis(2-hydroxyethyl) ethylenediamine.
Among the preferred amines making up b(ii) are the alkylene polyamines, including the polyalkylene polyamines. In another embodiment, the polyamine may be a hydroxyamine provided that the polyamine contains at least one condensable xe2x80x94Nxe2x80x94H group. Preferred polyamine reactants include triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and mixtures of polyamines such as the above-described xe2x80x9camine bottomsxe2x80x9d.
Preferred combinations of reactants for making the polyamine product include those in which reactant (b-i) is a polyhydric alcohol having three hydroxyl groups or an amino alcohol having two or more hydroxy groups and reactant (b-ii) is an alkylene polyamine having at least two primary nitrogen atoms and wherein the alkylene group contains 2 to about 10 carbon atoms.
The reaction is conducted in the presence of an acid catalyst at an elevated temperature. Catalysts useful for the purpose of this invention include mineral acids (mono, di- and poly basic acids) such as sulfuric acid and phosphoric acid; organophosphorus acids and organo sulfonic acids, alkali and alkaline earth partial salts of H3PO4 and H2SO4, such as NaHSO4, LiHSO4, KHSO4, NaH2PO4, LiH2PO4 and KH2PO4; CaHPO4, CaSO4 and MgHPO4; also Al2O3 and Zeolites. Phosphorus and phosphoric acids and their esters or partial esters are preferred Also useful as catalysts are materials which generate acids when treated in the reaction mixture, e.g., trialkylphosphites. Catalysts are subsequently neutralized with a metal-containing basic material such as alkali metal, especially sodium, hydroxides.
The amine condensates and methods of making the same are described in Steckel (U.S. Pat. No. 5,053,152) which is incorporated by reference for its disclosure to the condensates and methods of making.
Illustrative heterocycle precursors (III) which may react with an acid or acid derivative group to form heterocycles are aminoguanidine and salts thereof, semicarbazide, thiosemicarbazide, carbohydrazide and thiocarbohydrazide, as well as salts thereof such as aminoguanidine bicarbonate. The cyclization reactions which take place are exemplified by those disclosed in Angewandte Chemie, International Edition, 2, 459 (1963); Organic Syntheses, Coll. Vol. III, 95 (1955); and Chemical Abstracts, 57, 804i (1962), which are incorporated by reference for such disclosures. They may be illustrated as follows: 
Various other reactions may also form heterocycles. For example, the heterocycle or acyclic heterocycle precursor may react with an acid derivative such as an anhydride or ester. Also, a reaction may take place between an acid or acid derivative group and an active hydrogen-containing atom on the heterocycle formed from the acyclic heterocycle precursor; e.g., the 3-amino or ring NH group of a 3-amino-triazole.
Useful compositions of this invention may be prepared by reacting the carboxylic group containing intermediate with either of Hxe2x80x94W-alkylene-NH2 (II) and 
or salts thereof. Alternatively, the carboxylic group containing intermediate is reacted with both of Hxe2x80x94W-alkylene-NH2 (II) and 
simultaneously or consecutively in any order. When both of (II) and (III) are used, the typical reaction is with from about 20-40 mole % of (II) and from about 60-80 mole % of (III).
In yet another embodiment, the intermediate from the carboxylic acid or functional derivative thereof is reacted with both of at least one heterocycle precursor and at least one additional compound having at least one condensable Nxe2x80x94H group, simultaneously or consecutively, in any order.
The at least one additional compound is a reactant that does not form a heterocyclic group B under the conditions described herein.
In one embodiment, the additional compound is the reaction product of a hydrocarbyl substituted acid or anhydride having at least 30 carbon atoms in the hydrocarbyl group and an alkylene polyamine having 2 or 3 carbon atoms in each alkylene group. In another embodiment, the additional compound is a heterocyclic derivative of a fatty acid and an alkylene polyamine containing at least one nitrogen atom in the heterocyclic group.
Primary and secondary monoamines are also useful as additional compounds.
It is possible that the reaction of a carboxylic acid or derivative, such as the intermediate arising from reaction of the polymer (P) and the carboxylic reactant G), with a heterocycle precursor may, under certain conditions, afford substantial proportions of a non-heterocyclic product. For example, reaction with ethylene diamine or monoethanol amine may generate an amide; with semicarbazide a group of formula 
Non-heterocyclic groups of these kinds are included within the definition of the groups xe2x80x98Axe2x80x99 in the composition of Formula (I).
(D) The Hydrocarbyl Substituted Carboxylic Acid or Anhydride.
In still another embodiment, the reaction of the intermediate arising from reaction of (P) and (G) with the heterocycle precursor (C) is conducted, simultaneously or consecutively, with (D), at least one hydrocarbyl substituted carboxylic acid or anhydride. In this embodiment, typically from about 60% to about 80% of the heterocycle precursor is reacted with a hydrocarbyl substituted carboxylic acid or anhydride before reaction with the intermediate.
Reactant (D), a carboxylic acid or anhydride, may be mono- or polycarboxylic. Suitable carboxylic acids or anhydrides are hydrocarbyl substituted, preferably oil-soluble. These may be aromatic, cycloaliphatic and aliphatic acids. Preferably the hydrocarbyl substituent is aliphatic and contains at least 8 carbon atoms, more preferably at least about 30 carbon atoms. In another embodiment (D) comprises a mixture of hydrocarbyl substituted carboxylic acids or anhydrides wherein the mixture comprises aliphatic substituted carboxylic acids or anhydrides containing from about 12 to about 24 carbon atoms in the aliphatic substituent and aliphatic substituted carboxylic acids or anhydrides having at least about 40 carbon atoms in the aliphatic substituent.
Monocarboxylic acids have the formula RCOOH. R is a hydrocarbyl group, preferably an aliphatic group. Preferably, R contains from about 2 to about 500 carbon atoms. In one preferred embodiment, R is an aliphatic group containing from about 8 to about 24 carbon atoms, more often from about 12 to about 18 carbon atoms. Examples of such acids are caprylic, capric, palmitic, stearic, isostearic, oleic, linoleic, and behenic acids.
Another preferred group of monocarboxylic acids is prepared by the reaction of a polyolefin or a halogenated olefin polymer with acrylic acid or methacrylic acid.
Polycarboxylic acids may be illustrated by the general formula
Rxe2x80x94(COOH)m
wherein R is a hydrocarbyl group. R may be aliphatic or aromatic, including alkyl, alkenyl, aralkyl and alkaryl, including mixtures of acids containing aliphatic and aromatic groups. Preferably R is an aliphatic group, and preferably contains from about 5 to about 500 carbon atoms, more preferably from 16 to about 200 carbon atoms, even more preferably from about 30 to about 100 carbon atoms. The subscript xe2x80x98mxe2x80x99 is a number ranging from 2 to about 10, preferably 2 to about 4, more preferably 2 or 3. In an especially preferred embodiment m=2. Mixtures of such acids are also useful.
Patents describing useful aliphatic carboxylic acids or anhydrides and methods for preparing them include, among numerous others, U.S. Pat. No. 3,215,707 (Rense); U.S. Pat. No. 3,219,666 (Norman et al), U.S. Pat. No. 3,231,587 (Rense); U.S. Pat. No. 3,912,764 (Palmer); U.S. Pat. No. 4,110,349 (Cohen); and U.S. Pat. No. 4,234,435 (Meinhardt et al); and U.K. 1,440,219. These patents are hereby incorporated herein by reference for relevant disclosures contained therein.
In another preferred embodiment, the acid or anhydride (D) may contain from about 8 to 28 carbon atoms. When these are aliphatic acids, preferably predominantly linear acids, they tend to provide friction reducing characteristics to lubricating oils comprising the dispersant-viscosity improvers of this invention which incorporate such acids therein.
Another group of carboxylic reactants suitable as (D) comprises those obtained by reacting keto- or aldehydocarboxylic acids and functional derivatives thereof with olefinic reactants having molecular weight ranging from about 100 to 20,000, preferably aliphatic mono olefins having from 30 to about 200 carbon atoms. Representative of such materials are products obtained by reacting polyisobutylene ({overscore (M)}nxcx9c1000) with glyoxylic acid or the methyl ester, methyl hemiacetal thereof. Representative materials are described in European (EP) patent publications 0759443; 0759444; and 0759435.
Further carboxylic reactants suitable as (D) are those obtained by reacting aldehydo- or keto carboxylic acids and functional derivatives thereof with hydrocarbyl substituted, particularly C10-100 substituted hydroxy aromatic compounds, preferably phenols. Representative materials are described in U.S. Pat. Nos. 5,281,346; 5,356,546; and 5,336,278.
Other useful acids are hydrocarbyloxypolyoxyalkylenecarboxylic acids. Some examples include: lauryl-Oxe2x80x94(CH2CH2O)2.5xe2x80x94CH2CO2H; lauryl-Oxe2x80x94CH2CH2O)3.3CH2CO2H; lauryl-Oxe2x80x94(C3H6O)x(CH2CH2O)yCH2CO2H, wherein x=2-3 and y=1-2, and 2-octadecanyl-Oxe2x80x94(CH2CH2O)6CH2CO2H. Additionally, polyether alpha, omega-acids, such as 3,6,9-trioxaundecane-1,11-dioic acid and mixed polyether diacids available from Hoechst Chemie can also be incorporated to impart surface activity and polarity, and to affect morphology at low temperatures.
In one embodiment, the hydrocarbyloxypolyoxyalkylenecarboxylic acid is stearyl, preferably isostearyl, pentaethyleneglycolacetic acid,. Some of these acids are available commercially from Sandoz Chemical under the tradename Sandopan Acids.
Other acids useful as (D) are aromatic acids such as benzoic, salicylic, hydroxynaphthoic and heterocyclic acids, for example, pyridine dicarboxylic acid and pyrrolidone-5-carboxylic acid.
Polyacids from vegetable- and animal-sourced carboxylic compounds can be used. Dimer acids, made by the thermal coupling of unsaturated vegetable acids, are available from Emery, Westvaco, Unichema and other companies. Polyacid reaction products of unsaturated vegetable acids with acrylic acid and maleic anhydride are available from Westvaco under the product names Diacid 1550 and Tenax 2010, respectively. Another useful vegetable derived acid is 12-hydroxystearic acid.
Preferred are carboxylic acids, including polyolefin substituted succinic acids, succinic anhydrides, ester acids or lactone acids.
The following examples are intended to illustrate several compositions of this invention as well as means for preparing same. Unless indicated otherwise all parts are parts by weight, temperatures are in degrees Celsius, and pressures in millimeters mercury (mm Hg). Any filtrations are conducted using a diatomaceous earth filter aid. Analytical values are obtained by actual analysis. It is to be understood that these examples are not intended to limit the scope of the invention.